Adsorption States Research Articles

Research on the corrosion inhibition performance and mechanism of pyrimidine quaternary ammonium salt

PurposeAt present, research on the preparation of corrosion inhibitors using modified pyrimidine derivatives is still blank. The purpose of this study is to synthesize a new cationic mercaptopyrimidine derivative quaternary ammonium salt, known as DTEBTAC, that can be used as a corrosion inhibitor to slow down the metal corrosion problems encountered in oil and gas extraction processes.Design/methodology/approachA new corrosion inhibitor was synthesized by the reaction of anti-Markovnikov addition and nucleophilic substitution. The weight loss method was used to study the corrosion inhibition characteristics of synthetic corrosion inhibitors. Electrochemical and surface topography analyses were used to determine the type of inhibitor and the adsorption state formed on the surface of N80 steel. Molecular dynamics simulations and quantum chemistry calculations were used to investigate the synthetic corrosion inhibitor’s molecular structure and corrosion inhibition mechanisms.FindingsThe results of the weight loss method show that when the dosage of DTEBTAC is 1%, the corrosion rate of N80 steel in hydrochloric acid solution at 90? is 3.3325 g m-2 h-1. Electrochemical and surface morphology analysis show that DTEBTAC can form a protective layer on the surface of N80 steel, and is a hybrid corrosion inhibitor that can inhibit the main anode. Quantum chemical parameter calculation shows that DTEBTAC has a better corrosion inhibition effect than DTP. The molecular dynamics simulation results show that DTEBTAC has stronger binding energy than DTP, and forms a network packing structure through hydrogen bonding, and the adsorption stability is enhanced.Originality/valueA novel cationic mercaptopyrimidine derivative quaternium-ammonium salt corrosion inhibitor was designed and provided. Compared with the prior art, the preparation method of the synthesized mercaptopyrimidine derivative quaternary ammonium salt corrosion inhibitor is simple, and the presence of nitrogen-positive ions, sulfur atoms and nitrogen-rich atoms has an obvious corrosion inhibition effect, which can be used to inhibit metal corrosion during oil and gas field exploitation. It not only expands the application field of new materials but also provides a new idea for the research and development of new corrosion inhibitors.

Determination of ammonia nitrogen by surface-enhanced Raman spectroscopy and DFT studies

Ammonia nitrogen is one of the most important indicators for evaluating the quality of water bodies. It is very difficult to determine ammonia nitrogen directly by Surface-enhanced Raman spectroscopy (SERS) in practice. In order to realize SERS determination of ammonia nitrogen, in this paper, SERS combined with density functional theory (DFT) was used to investigate why ammonia nitrogen needs to be derivatized to hexamethylenetetramine (HMTA) and why HMTA can be determined using SERS. The molecular electrostatic potential (MEP) results exhibit that there was no adsorption site on the surface of ammonia nitrogen, whereas its derivate HMTA had four available adsorption sites. This provides a basic guarantee for the SERS detection of HMTA. The molecular adsorption state of HMTA on the gold nanoparticles surface was concluded from the binding energies, the bond length, and the Raman activity spectra. Among them, the HMTA-Au4 complex has the lowest bond energy (−586.873 Kcal/mol) and the shortest bond length (2.161 Å), which is the most stable state and its Raman activity spectrum is the closest to the experimental data. Calculations results of frontier molecular orbital (FMO) demonstrate that the energy gap of HMTA and HMTA-Au4 complex are 0.30258 eV and 0.10947 eV, respectively, with a really obvious difference between them, which indicates that the HMAT-Au4 complex possessed higher chemical reactivity. In addition, charge transfer phenomenon on the MEP of HMTA-Au4 complex was deduced due to the change in the symmetry of its charge distribution, which can be explained the mechanism of chemical enhancement in the detection of HMTA by SERS. The selective enhancement at 1048 cm−1 peaks in theoretical spectrum and at 1044 peaks cm−1 in experimental spectrum provided theoretical and practical basis for indirect determination of ammonia nitrogen by SERS. The obtained results will help to better understand the reasons why some components are difficult to be directly determined by SERS, and why these components need to be derivatized. It provides a new method for components that are difficult to detect by SERS.

The occurrences and mobility of shale oil in the pore space of terrestrial shale

Movable oil, the critical factor for shale oil enrichment and effective production, is influenced by the pore structure and shale oil occurrence state. However, the pore spaces storing movable oil, the occurrence state of shale oil, and the lower flowing pore size for shale oil remained unclear. To address this knowledge gap, we chose the lacustrine organic-rich Chang7 shale of the Ordos Basin as the research target. By combining gas adsorption techniques (nitrogen and carbon dioxide) with Soxhlet Extraction, we investigated the pore structure alteration of Chang7 shale after Soxhlet Extraction. Based on a comprehensive analysis of mineralogical composition, TOC, and shale oil components, we discussed the pore space in which shale oil exists. Then, we established a slit-shaped clay model and clarified the occurrence state of multi-component shale oil in the pore space with the help of molecular simulation. Our investigation revealed that (1) Chang7 shale can be categorized into three distinct types. Type I, characterized by a high clay mineral content, possesses the greatest SSA and PV and has the highest abundance of movable oil, partially filling the “ink-bottle”-type pores. Shale oil in Type II and III shales mainly exists within slit-type pores. (2) The pore space of Chang7 shale is primarily comprised of mesopores rather than micropores. Moreover, mesopores’ PV and SSA are predominantly governed by clay minerals rather than organic matter. (3) A threshold pore size of 10 nm significantly impacts the occurrence state of shale oil in the Chang7 shale. Beyond this threshold, free oil accounts for over 80% of the total. Chang7 shale oil within micropores (<2 nm) is predominantly asphaltene, existing in an adsorbed state. Within pores sized 2 to 10 nm, shale oil is present in both adsorbed and free states, and the proportion of free-state shale oil increases with the pore size. Free-state shale oil prevails in pores exceeding 10 nm, with a smaller fraction adsorbed onto organic matter and mineral surfaces. Thus, we recommend adopting 10 nm as the lower flowing pore size limit for Chang7 shale.

Consequences of Pore Polarity and Solvent Structure on Epoxide Ring-Opening in Lewis and Brønsted Acid Zeolites.

The structure of solvent molecules within zeolite pores influences the rates and selectivities of catalytic reactions by altering the free energies of reactive species. Here, we examine the consequences of these effects on the kinetics and thermodynamics of 1,2-epoxybutane (C4H8O) ring-opening with methanol (CH3OH) in acetonitrile (CH3CN) cosolvent over Lewis acidic (Zr-BEA) and Brønsted acidic (Al-BEA) zeolites of varying (SiOH) x density. Despite ostensibly identical reaction mechanisms across materials, turnover rates depend differently on (SiOH) x density between acid types. (SiOH) x -rich Zr-BEA (Zr-BEA-OH) provides ∼10 times greater rates than a (SiOH) x -poor material (Zr-BEA-F), while Al-BEA-OH and Al-BEA-F give turnover rates within a factor of 2. Zr-BEA-OH shows more positive activation enthalpies and entropies than Zr-BEA-F across the range of [CH3OH], which reflect the displacement of solvent molecules and lead to greater rates in Zr-BEA-OH due to the dominant role of entropic gains. Measurements of the density and composition of solvent within the pores show that the (SiOH) x nests within Zr-BEA-OH promote hydrogen-bonded solvent structures distinct from Zr-BEA-F, while the Brønsted acid sites confer interactions similar to (SiOH) x nests and give solvent structures within Al-BEA-F that resemble those within Al-BEA-OH. Correlations between apparent activation enthalpies and C4H8O adsorption enthalpies show that interactions with solvent molecules give proportional changes to both C4H8O adsorption and ring-opening transition state formation. The differences in intrapore environment carry consequences for both rates and regioselectivities of epoxide ring-opening, as demonstrated by product regioselectivities that increase by a factor of 3 in response to changes in solvent composition and the type of acid site in the *BEA structure (i.e., Lewis or Brønsted). These results demonstrate the ability to control rates, regioselectivities, and adsorption thermodynamics relevant for industrially relevant liquid-phase reactions through the design of noncovalent interactions among solvating molecules, reactive species, and (SiOH) x functions.

Effect of nitrogen-containing groups on the reduction of copper ions: In situ Raman and AIMD

In situ Raman spectroscopy and ab initio molecular dynamics (AIMD) were utilized to observe and analyze the micro-scale variations of levelers on the cathode surface. The cathodic polarization and charge transfer resistance of the three electroplating systems were examined using electrochemical methods. The throwing power of the printed circuit board coating and the nucleation changes at various times were investigated using an OLYMPUS confocal laser microscope and a scanning electron microscope. Based on the first-principles and AIMD calculations, the energy gaps, adsorption energies, and dynamic changes over 20 ps for the three levelers were determined, and the molecular mechanisms of action on the copper surface were analyzed to demonstrate alterations in the coating thickness. Experimental and theoretical results indicate that 2-thiazole-2-thiol possesses the strongest inhibitory energy, significantly repelling copper ions from migrating to the far end. On the surface, 4,6-dimethyl-2-pyrimidinethiol decomposes to form nitrogenous and sulfurous groups, which inhibit and adsorb copper ions. The adsorption states of the three levelers were thoroughly validated using Raman spectroscopy, corroborating the AIMD simulation results.

Built‐In Trimodal Molecular Interaction Effect Enables Interface‐Compatible and Temperature‐Tolerance Aqueous Zinc Batteries

AbstractAqueous zinc‐ion batteries compatible with a wide temperature range and long cycle lifespan show great application prospects but are greatly limited by the unstable electrode‐electrolyte interfaces and mismatched electrolytes. This report presents the pathway of succinamic acid (SA) additive‐induced built‐in trimodal molecular interaction for constructing sustainable aqueous zinc batteries. As confirmed, such trimodal molecular interaction falls into the following patterns: the binding state of the H─F bond between SA and polyvinylidene fluoride (PVDF) binder, the micellar aggregation state in aqueous electrolyte, and the spontaneous adsorption state at Zn anode–electrolyte interface. Benefiting from the above synergistic effect, the Zn electrode shows a highly reversible deposition/stripping behavior over the wide temperature range (−10–50 °C) when paired with the optimized electrolyte. Specially, an impressive 3530 h‐cycle lifespan of the Zn symmetrical cell is achieved at the conditions of 1 mA cm−2 and 1 mAh cm−2. Beyond that, significantly improved storage capability and cycle performance are demonstrated in both aqueous Zn‐MnO2 and Zn‐I2 batteries. Given the good balance between the working temperature range, ionic conductivity, and Zn2+ transfer number of this trace molecule‐mediated electrolyte, this design paradigm provides new insights into developing advanced aqueous batteries, including but not limited to zinc‐based systems.

Unconventional hcp/fcc Nickel Heteronanocrystal with Asymmetric Convex Sites Boosts Hydrogen Oxidation

Developing non‐platinum group metal catalysts for the sluggish hydrogen oxidation reaction (HOR) is critical for alkaline fuel cells. To date, Ni‐based materials are the most promising candidates but still suffer from insufficient performance. Herein, we report an unconventional hcp/fcc Ni (u‐hcp/fcc Ni) heteronanocrystal with multiple epitaxial hcp/fcc heterointerfaces and coherent twin boundaries, generating rugged surfaces with plenty of asymmetric convex sites. Systematic analyses discover that such convex sites enable the adsorption of *H in unusual bridge positions with weakened binding energy, circumventing the over‐strong *H adsorption on traditional hollow positions, and simultaneously stabilizing interfacial *H2O. It thus synergistically optimizes the HOR thermodynamic process as well as reduces the kinetic barrier of the rate‐determining Volmer step. Consequently, the developed u‐hcp/fcc Ni exhibits the top‐rank alkaline HOR activity with a mass activity of 40.6 mA mgNi‐1 (6.3 times higher than fcc Ni control) together with superior stability and high CO‐tolerance. These results provide a paradigm for designing high‐performance catalysts by shifting the adsorption state of intermediates through configuring surface sites.

Pore-scale probing CO2 huff-n-puff in extracting shale oil from different types of pores using online T1–T2 nuclear magnetic resonance spectroscopy

CO2 huff-n-puff shows great potential to promote shale oil recovery after primary depletion. However, the extracting process of shale oil residing in different types of pores induced by the injected CO2 remains unclear. Moreover, how to saturate shale core samples with oil is still an experimental challenge, and needs a recommended procedure. These issues significantly impede probing CO2 huff-n-puff in extracting shale oil as a means of enhanced oil recovery (EOR) processes. In this paper, the oil saturation process of shale core samples and their CO2 extraction response with respect to pore types were investigated using online T1–T2 nuclear magnetic resonance (NMR) spectroscopy. The results indicated that the oil saturation of shale core samples rapidly increased in the first 16 days under the conditions of 60 °C and 30 MPa and then tended to plateau. The maximum oil saturation could reach 46.2% after a vacuum and pressurization duration of 20 days. After saturation, three distinct regions were identified on the T1–T2 NMR spectra of the shale core samples, corresponding to kerogen, organic pores (OPs), and inorganic pores (IPs), respectively. The oil trapped in IPs was the primary target for CO2 huff-n-puff in shale with a maximum cumulative oil recovery (COR) of 70% original oil in place (OOIP) after three cycles, while the oil trapped in OPs and kerogen presented challenges for extraction (COR < 24.2% OOIP in OPs and almost none for kerogen). CO2 preferentially extracted the accessible oil trapped in large IPs, while due to the tiny pores and strong affinity of oil-wet walls, the oil saturated in OPs mainly existed in an adsorbed state, leading to an insignificant COR. Furthermore, COR demonstrated a linear increasing tendency with soaking pressure, even when the pressure noticeably exceeded the minimum miscible pressure, implying that the formation of a miscible phase between CO2 and oil was not the primary drive for CO2 huff-n-puff in shale.

The pH-dependent role of different manganese oxides in the fate of arsenic during microbial reduction of arsenate-bearing goethite

Manganese oxides reduce arsenic (As) toxicity by promoting aqueous-phase As(III) oxidation and immobilization in natural aquatic ecosystems. In anaerobic water-sediment systems, arsenic exists both in a free state in the liquid phase and in an adsorbed state on iron (Fe) minerals. However, the influence of different manganese oxides on the fate of As in this system remains unclear. Therefore, in this study, we constructed an anaerobic microbial As(V) reduction environment and investigated the effects of three different manganese oxides on the fate of both aqueous-phase and goethite-adsorbed As under different pH conditions. The results showed that δ-MnO2 had a superior As(III) oxidation ability in both aqueous and solid phase due not only to the higher SSA, but also to its wrinkled crystalline morphology, less favorable structure for bacterial reduction, structure conducive to ion exchange, and less interference caused by the formation of secondary Fe-minerals compared to α-MnO2 and γ-MnO2. Regarding aqueous-phase As, δ-MnO2, α-MnO2, and γ-MnO2 required an alkaline condition (pH 9) to exhibit their strongest As(III) oxidation and immobilization capability. For goethite-adsorbed As, under microbial-reducing conditions, all manganese oxides had the highest As immobilization effect in neutral pH environments and the strongest As oxidation effect in alkaline environments. This was because at pH 7, Fe(II) and Mn(II) formed hydrated complexes, which was more favorable for As adsorption. At pH 9, the negatively charged state of goethite hindered As adsorption but promoted the adsorption and oxidation of As by the manganese oxides. Our research offers new insights for optimizing As removal from water using various manganese oxides and for controlling the mobilization of As in water-sediment system under different pH conditions.

Bi2O3@reduced graphene oxide and NiCo2@Ni3Co electrodes for all-electrodeposited high-performance supercapacitors

A novel α-Bi2O3@reduced graphene oxide (rGO) composite negative electrode is designed using an electrodeposition technique, exhibiting an activation process during the first 100 charge-discharge cycles. The bismuth compounds in an initial adsorbed state gradually transformed into a dissolved state, resulting in a distinctive morphological change and the formation of a porous nanosheet structure. At a current density of 1 A/g, the α-Bi2O3@rGO achieves a specific capacitance of 1144 F/g (317 mAh/g), representing 92.18 % of its theoretical value. Even when the current density is increased by 20 times, the capacitance still maintains at 91.71 %. Additionally, a multi-layered composite cathode of NiCo2@Ni3Co is prepared. Based on these two electrodes, an all-electrodeposited soft-packaged supercapacitor (AESPS) is assembled, reaching an energy density of 107.8 Wh/kg at a power density of 800 W/kg, and 73.8 Wh/kg at 16 kW/kg. These outstanding electrochemical performances strongly demonstrate their potential in novel energy storage devices.

Selectivity towards xylene and ethylbenzene detection induced by synergistic effects of Sm3+ and Yb3+ on p-n heterostructure nanorods of Co3O4-In2O3

The synergistic effects of Sm3+/Yb3+ on a p-n ternary heterostructure of Co3O4-In2O3 (Co-In) nanorods, prepared by a hydrothermal approach for the construction of a gas sensor with unique sensing characteristics are reported. The intrinsic characteristics of the ternary heterostructures, such as surface adsorption states, crystal structures, and chemical states, were analyzed. The sensing analyses demonstrated that amongst the Sm3+/Yb3+ incorporated in the Co-In surface, the Co-In 0.25 mol.% Sm3+ displayed superior gas sensing toward ethylbenzene gas at a low operational temperature (i.e., 75 °C). At 100 °C, the precise selectivity toward xylene vapour was witnessed for the Co-In: 0.25 mol.% YbO. At lower gas concentration ranges of 0.08–5 ppm of acetone, 0.5–5 ppm of benzene, and 5–10 ppm of toluene, ethylbenzene, and xylene, the Co-In: 0.25 mol.% YbO was more sensitive to 0.08 ppm of acetone at 75 °C. Collective materials characterization and testing of the device analyses demonstrated that the observed sensing enhancement is primarily ascribed to the stronger capacity of oxygen-adsorption on Co-In: 0.25 mol.%:YbO. The depletion layer width strongly increased due to the formation of the multi-ternary junctions between the Co3O4, In2O3, and Yb2O3. The VO-rich Co3O4 has favoured the adsorption of xylene. The lower detection of acetone at ppb was associated with the preferred facet of acetone detection in comparison to xylene. The prospective sensing mechanism of the ternary heterostructure-based sensors has also been proposed.

TiO2 thermal stress deformation induced to promote photocatalytic CO2 reduction

Semiconductor photocatalytic reduction of CO2 is an effective means to achieve the goal of double carbon. TiO2 has received extensive attention as an excellent photocatalyst, but the adsorption of CO2 on the surface of TiO2 is not stable, which greatly inhibits the yield and selectivity of reduction products. In this work, wollastonite was used to reduce the melting temperature of TiO2 and in turn induce thermal stress deformation on the surface of the TiO2 lattice. Characterization and DFT results certified that the lattice stress deformation caused by the contraction of oxygen vacancy enables TiO2 to obtain better carrier transport efficiency and lower activation energy barrier, and also stabilizes the adsorption state of CO2 on the surface of TiO2 crystal, which effectively improved the reduction yield and selectivity of CO2. The CO yield is increased by 5.1 times, reaching up to 2.09 μmolg-1h−1, and the CO selectivity is as high as 91 %. These findings provide valuable insights for the development of efficient and selective photocatalysts for carbon dioxide transformation and pave the way for novel avenues in this research field.

Effect of lipid‐mediated moisture status on casein characteristic in two types of milk powders during accelerated storage

AbstractThis study aims to investigate the relationship between casein oxidation and moisture status in the presence of milk fat to clarify the role of fat on water in milk powder. The results showed that at the same water activity (aw), the faster oxidation of whole milk powder (WMP) is attributed to the high proportion of free water and immobilized water in them, indicating that the adsorption of milk fat mainly depended on multilayer water and the entrapped water. In the diffusion‐limited reaction, changes in water state affected more than radicals on casein oxidation. Glass transition temperature (Tg) was also affected by the water state of lipid adsorption. At low aw (&lt;0.4), the water content of WMP and skim milk powder (SMP) was similar, but the Tg of WMP was significantly lower than SMP, especially when aw was 0.33, its Tg was &lt;0. It suggested that water state rather than water content was the main factor affecting Tg. Especially, because the mobile water absorbed by milk fat in WMP reduced Tg, which further led to the acceleration of lactose crystallization, casein oxidative aggregation, and Maillard reaction.

Effect of alkyl glucoside concentration on functional group structure and adsorption characteristics of anthracite.

To investigate the influence of different concentrations of surfactants on the adsorption of anthracite, the nonionic surfactant alkyl polyglucoside (APG) was selected. The study examined the adsorption characteristics of different concentrations of APG on the surface of anthracite. The results revealed the existence of two modes of APG adsorption on anthracite. Under the action of 0.06 wt% APG, APG was found to adsorb in a monolayer state on the anthracite surface, with a saturation adsorption capacity of 20.06mg/g. When the solution concentration exceeded 0.14 wt%, APG exhibited a double-layer saturation adsorption state on anthracite, with a saturation adsorption capacity of 71.71mg/g. Molecular dynamics simulations complemented these findings, demonstrating that low concentrations of APG could reduce the mobility of water molecules and enhance the hydrophilicity of anthracite. With an increase in the number of APG molecules, multi-layer adsorption occurred on the anthracite surface, making it more hydrophobic. Therefore, the differences in wettability of anthracite induced by different concentrations of APG were primarily attributed to the spatial distribution of the surfactant at the water/coal interface. This study analyzed the adsorption capacity of the surfactant through adsorption experiments and Fourier-transform infrared spectroscopy (FTIR) experiments. Molecular dynamics simulations were conducted to construct six concentration levels of water/APG/anthracite systems. Various aspects, including APG adsorption configurations, interaction energies, relative concentrations of each component, and the diffusion coefficient of water molecules, were discussed to elucidate the reasons for the differential wettability of anthracite induced by different concentrations of APG.

Co-Adsorption of Alcohols and Water in JUK-8 Studied Using Quasi-Equilibrated Thermodesorption.

JUK-8 ([Zn(oba)(pip)]n, oba2- = 4,4'-oxybis(benzenedicarboxylate), pip = 4-pyridyl-functionalized benzene-1,3-dicarbohydrazide) is a hydrolytically stable flexible metal-organic framework. Owing to its unusual adsorptive properties, JUK-8 can be considered as a promising sensing material for construction of detectors of volatile organic compounds (VOCs) in air. Quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) is a versatile method dedicated to characterization of porous materials. In this work, QE-TPDA was employed to study co-adsorption of water and selected alcohols in JUK-8. For the first time an infrared detector sensitive to organic compounds was used in the QE-TPDA measurements, allowing the study of the influence of water vapor on sorption of VOCs. The QE-TPDA profiles of the studied alcohols, exhibiting two desorption maxima and two adsorption minima, are consistent with the standard sorption isotherms, revealing a two-step adsorption-desorption mechanism. The profiles recorded in the presence of water are noticeably changed in different ways for different alcohols. While at low relative humidity (RH) (ca. 20%) the low temperature adsorption states of ethanol and 1-propanol were only slightly destabilized, for 2-propanol almost complete suppression of adsorption was observed. The results found for moderate RH levels (ca. 50%) indicated that the opening of the JUK-8 structure, responsible for its breathing behavior, was followed by the filling of the just generated pores with a water-alcohol mixture.

Effects of surfactant types on anthracite dust wettability: Experimental and molecular simulations

To study the wetting mechanism of surfactants at the solid–liquid interface of anthracite, a combination of experiments and molecular simulation was used to explore the adsorption and wetting processes of four surfactants, namely, fatty alcohol polyoxyethylene ether N = 9 (AEO9), Triton X-100, rapid penetrant T (PRT), and sodium alkyl ether sulfate (AES) on anthracite. The wetting mechanism of surfactants on anthracite was analyzed at both macroscopic and microscopic levels by surface tension, contact angle, settling time, and changes in surface morphology and functional groups on the anthracite surface. The presence of OH-π and C = O was determined to significantly enhance anthracite wettability. The anthracite/surfactant/water system was constructed from a microscopic perspective, and the interaction energies, relative concentration distributions along the Z-axis, diffusion coefficient (D) of water molecules, radial distribution functions (RDF) of hydrophilic groups and water molecules, and coordination numbers of the components were analyzed. The results show that the wetting effect depends on the adsorption state of the surfactant at the anthracite/water interface and the strength of the interaction between the surfactant and water molecules. The addition of surfactants enhances the adsorption thickness of water molecules along the Z-axis and generates more hydrogen bonds, which play a role in fixing water molecules and lead to a decrease in the D of water molecules. RPT forms the highest number of hydrogen bonds with water molecules and has the lowest D of 0.479 × 10-5 cm2/s, indicating strong wetting ability. The RDF of O atoms in surfactants and water molecules shows a similar trend, with two peaks one strong and one weak. The coordination numbers are 1.356, 1.057, 1.003, and 0.903, respectively. The final wettability of the surfactant on the anthracite depends on the synergistic interaction between the oxygen functional groups (OGs) as compared to the coordination number of the individual OGs.

Theoretical calculations and experimental verification of carbon dioxide reduction electrocatalyzed by metalloporphyrin

Metal-functionalized porphyrin-like graphene structures are promising electrocatalysts for carbon dioxide reduction reaction (CO2RR) as their metal centers can modulate activity. Yet, the role of metal center of metalloporphyrins (MTPPs) in CO2 reaction activity is still lacking deep understanding. Here, CO2RR mechanism on MTPPs with five different metal centers (M = Fe, Co, Cu, Zn and Ni) are examined by first-principles calculations. The *COOH formation is the rate determined step on the five MTPP structures, and the CoTPP exhibits the best CO2RR activity while ZnTPP and NiTPP are the worst, which is also verified by our experiment. The CO2RR activity is controlled by adsorption states of intermediates (*CO, *COOH), i.e., chemisorption (e.g., on CoTPP) and physisorption (on ZnTPP and NiTPP) of intermediates will lead to good and poor activity, respectively. The deeper the d-band center of the porphyrin ring complexed metal atom, the weaker bonding of MTPP with CO and COOH. Theoretical calculations and experimental results indicate that MTPPs with Co and Fe centers lead to a reduction in the energy barriers for the two uphill reaction steps in the electrocatalytic CO2 reduction process, thereby enhancing CO2 reduction electrocatalytic activity. Faradaic efficiency of CO is correlated with the reaction energy barrier of the first proton-coupled electron reduction process, displaying a strong linear correlation. This work provides a fundamental understanding of MTPPs used as electrocatalysts for CO2RR.

Comparative analysis of CO2 and N2 adsorption on zeolite 4A: Thermodynamics parameters and site energy distribution investigations

Adsorption equilibrium data for CO2 and N2 on zeolite 4A were volumetrically measured at temperatures ranging from 278 K to 328 K and gas pressures up to 4 MPa. The experimental data was correlated using the high-pressure Langmuir, Sips, and DA adsorption isotherm models. The high-pressure DA model was found to be the optimal model for describing the adsorption isotherms on basis of nonlinear regression analysis. Subsequently, the thermodynamic parameters, including isosteric heat of adsorption (Hst), adsorption phase specific heat capacity (cpa), adsorption phase entropy (sa), and enthalpy (ha), considering the actual adsorption state, were estimated. The results demonstrate that the adsorption of CO2 on zeolite 4A is greater than that of N2. The higher Hst and ha values and the lower sa values of CO2 compared to N2, suggest a stronger surface interaction of CO2 with zeolite 4A, resulting in a more ordered arrangement of CO2 molecules than N2. Site energy distribution theory analysis indicates that less energy is required for CO2 adsorption and greater site energy heterogeneity of CO2 than those of N2 on zeolite 4A. The obtained results evidence that the studied zeolite 4A could be a promising candidate adsorbent for greenhouse gas capture.

Control of Biological Surface States on Chlorine-Doped Amorphous Silica Particles and Their Effective Absorptive Ability for Antibody Protein.

Amorphous silica particles (ASPs) have low biotoxicity and are used in foodstuffs; however, the adsorption states of proteins on their surfaces have not yet been clarified. If the adsorption states can be clarified and controlled, then a wide range of biological and medical applications can be expected. The conventional amorphous silica particles have the problem of protein adsorption due to the strong interaction with their dense silanol groups and denaturation. In this study, the surfaces of amorphous silica particles with a lower silanol group density were modified with a small amount of chlorine during the synthesis process to form a specific surface layer by adsorbing water molecules and ions in the biological fluid, thereby controlling the protein adsorption state. Specifically, the hydration state on the surface of the amorphous silica particles containing trace amounts of chlorine was evaluated, and the surface layer (especially the hydration state) for the adsorption of antibody proteins while maintaining their steric structures was evaluated and discussed. The results showed that the inclusion of trace amounts of chlorine increased the silanol groups and Si-Cl bonds in the topmost surface layer of the particles, thereby inducing the adsorption of ions and water molecules in the biological fluid. Then, it was found that a novel surface layer was formed by the effective adsorption of Na and phosphate ions, which would change the proportion of the components in the hydration layer. In particular, the proportion of the free water component increased by 21% with the doping of chlorine. Antibody proteins were effectively adsorbed on the particles doped with trace amounts of chlorine, and their steric adsorption states were evaluated. It was found that the proteins were clearly adsorbed and maintained the steric state of their secondary structure. In the immunoreactivity tests using streptavidin and biotin, biotin bound to the chlorine-doped particles showed efficient reactivity. In conclusion, this study is the first to discover the surface layer of the amorphous silica particles to maintain the steric structures of adsorbed proteins, which is expected to be used as a carrier particle for antibody test kits and immunochromatography.

Kinetic analysis of monomolecular cracking of normal Alkanes (C4[sbnd]C6) over Brønsted Acid site of Zeolitic type catalyst with energetic evaluation of transition states using Quantum-Chemical modeling

The work aims to determine the kinetic parameters of reactions for production of light olefins via catalytic cracking reactions of C4–C6 n-alkanes based on the energy characteristics of the transition state using quantum chemical calculations. Cracking reactions of C4–C6 n-alkanes proceed via protolytic mechanism on the Brønsted acid sites of zeolite-containing catalysts. For kinetic studies in this work, the thermochemical parameters of the intermediate stages, including hydrocarbon adsorption and transition state were determined, then the activation energies and rate constants were determined over the temperature range of catalytic cracking process from 773 to 903 K (500–630 °C).The results showed that DFT method in combination with B3LYP and ωB97X-D functionals, and 3–21 G basis demonstrated quite high accuracy in determining thermochemical parameters, including enthalpy, entropy and Gibbs free energy at both energetic levels of adsorption and transition state. Then, modeling continued by calculations of activation energies and rate constants of reactions. Obtained kinetic parameters made it possible to determine the reactivity of hydrocarbons with different chain length. It was obtained that the rate constants of butane cracking reactions with the formation of ethylene are 54–90 times higher than the formation of propylene. The rate constants of pentane cracking reactions with the formation of butylene are on average 5 times higher than the formation of propylene. The rate constants for hexane cracking reactions with the formation of butylene are 2.9–3.7 times higher compared to the formation of propylene.